WO2005121227A1 - Film de résine - Google Patents

Film de résine Download PDF

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Publication number
WO2005121227A1
WO2005121227A1 PCT/JP2005/010896 JP2005010896W WO2005121227A1 WO 2005121227 A1 WO2005121227 A1 WO 2005121227A1 JP 2005010896 W JP2005010896 W JP 2005010896W WO 2005121227 A1 WO2005121227 A1 WO 2005121227A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin film
film
acetic acid
mass
resin
Prior art date
Application number
PCT/JP2005/010896
Other languages
English (en)
Japanese (ja)
Inventor
Tokuo Okada
Ichiro Aoki
Yorinobu Ishii
Original Assignee
Bridgestone Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corporation filed Critical Bridgestone Corporation
Priority to JP2006514611A priority Critical patent/JPWO2005121227A1/ja
Priority to CN2005800186508A priority patent/CN1997688B/zh
Priority to US11/570,085 priority patent/US20070259998A1/en
Priority to EP05751284A priority patent/EP1783159B1/fr
Publication of WO2005121227A1 publication Critical patent/WO2005121227A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a resin film advantageously used for a solar cell, a laminated glass including a metal layer, an organic glass, and the like.
  • a solar cell is provided with a sealing film of an ethylene monoacetate copolymer (EVA) film between a glass substrate as a front-side transparent protective member on the light-receiving side and a back-side protective member (back cover).
  • EVA ethylene monoacetate copolymer
  • a glass substrate In such a solar cell, a glass substrate, an EVA film for a sealing film, a silicon power generation element, an EVA film for a sealing film, and a pack power layer are laminated in this order, and the EVA is heated and melted and crosslinked. It is manufactured by bonding and integrating by curing.
  • the EVA film contains vinyl acetate as a component thereof, it tends to be hydrolyzed with time due to permeation of moisture or water at a high temperature to produce acetic acid. Yes (and also originally containing trace amounts of acetic acid), it was found that such acetic acid accelerates the generation of ⁇ by contact with internal conductors and electrodes.
  • Such EVA films are also used for laminated glass such as automobile windshields.
  • Laminated glass generally has a structure in which a transparent adhesive layer (intermediate film) made of an organic resin is sandwiched between glass plates (or between a glass and a plastic plate). In recent years, laminated glass has been deposited between the glass and the EVA film.
  • Laminated glass for heat ray reflection with a metal film inserted has also been increasingly used. It was also found that such a vapor-deposited metal film also promotes the generation of ⁇ in the metal film by acetic acid generated from the EVA film, as described above. The demand for such heat-reflecting glass and laminated glass is also expanding for use in buildings and the like.
  • EVA films used for the above-mentioned applications basically require a high degree of transparency. Therefore, a film which is transparent while preventing the occurrence of the above 1 is desired.
  • an object of the present invention which has been made in view of the above points, is to provide a resin film which does not generate acetic acid by being hydrolyzed with time due to environmental changes or the like, and is excellent in transparency.
  • Another object of the present invention is to provide a resin film having excellent durability and transparency suitable for a sealing film of a solar cell and a transparent adhesive layer such as laminated glass.
  • the present invention relates to a resin film containing an ethylene Z-vinyl acetate copolymer, wherein the resin film is left for 100 hours in an environment of 85 ° C. and a relative humidity of 85%, and then boiled with water.
  • Acetic acid extracted by heating and refluxing is 200 ppm or less (especially 100 ppm or less) in the resin film.
  • the amount of acetic acid extracted by water is generally considered to be correlated with the degree of corrosion.
  • the ethylene / butyl acetate copolymer is cross-linked by a cross-linking agent, and cross-linked by a cross-linking aid. It is preferred that Further, it preferably contains a silane coupling agent. The use of these is generally advantageous for suppressing the generation of acetic acid.
  • the content of the crosslinking agent is preferably in the range of 0.1 to 2% by mass, and particularly preferably in the range of 0.1 to 1% by mass, based on the ethylene Z-butyl acetate copolymer.
  • Mainly, vinyl ethylene acetate These amounts vary depending on the butyl acetate content of the copolymer. Use in such a range is generally advantageous for improving transparency and suppressing generation of sulfuric acid.
  • the amount of the crosslinking agent in the present invention is particularly preferably 1% by mass or less. This is because if too much cross-linking agent is added, the curing time is shortened, but air bubbles (possibly derived from acetic acid) are likely to be generated in the EVA, which impairs transparency. .
  • the resin film of the present invention may be prepared by heating the film (about 1 g) at 160 ° (for 30 minutes, and then reducing the film weight by 2.0% by mass or less). It is also preferable to add a crosslinking aid to promote crosslinking.
  • 0.1 to 2% by weight ranging content of the crosslinking aid is relative Echiren'no acetate Bulle copolymer, especially 0. Range ⁇ mass 0/0 are preferred. These amounts mainly vary depending on the vinylinole acetate content of the ethylene Z vinyl acetate copolymer. Use in such a range is generally advantageous for improving transparency and suppressing generation of acetic acid.
  • the vinyl acetate content of the ethylenenoacetate butyl copolymer is 25 to 29 mass. / 0 , especially 25-27 mass. / 0 is preferred. Acetic acid generation is suppressed and transparency can be ensured.
  • the haze is preferably 3 or less (especially 1 or less).
  • the crosslinking aid is triaryl isocyanurate.
  • the cross-linking agent is preferably 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 1,1-bis (t-butylperoxy) -13,3,5-trimethinolecyclohexane.
  • the film of the present invention when used as a sealing film for a solar cell, laminated glass, or the like, contains a benzotriazole-based compound in order to prevent the occurrence of corrosion such as ⁇ against the metal inside the film. Is preferred.
  • the resin film according to the present invention has a low acetic acid content and its generation with time is small, so that when this film comes into contact with a metal, it is almost impossible to corrode the metal. Not really. Furthermore, the resin film of the present invention has low haze and high transparency, and can be advantageously used in applications where high transparency is required to be maintained without corroding metals. .
  • the resin film of the present invention when used as a sealing film for a silicon power generation element of a solar cell, the generation of internal conductors and electrodes due to moisture or water permeation at high temperatures or the like can be reduced to an acetate. It can be prevented by suppressing the occurrence of Also, in a laminated glass for heat ray reflection in which a vapor-deposited metal film is inserted between the glass and the EVA film, it is possible to suppress the generation of the color of the metal film as described above. Therefore, it can be used particularly advantageously for these applications. Further, the resin film of the present invention can be advantageously used in any field where the film comes into contact with metal. Brief Description of Drawings
  • FIG. 2 is a cross-sectional view showing a basic configuration when the resin film of the present invention is used for a solar cell.
  • FIG. 3 is a cross-sectional view showing a basic configuration when the resin film of the present invention is used for a laminated glass.
  • the resin film of the present invention is a film containing an ethylene-vinyl acetate copolymer as a main component and in which the generation of acid is sufficiently suppressed.
  • the resin film of the present invention suppresses the generation of acetic acid, when used as a sealing film for a silicon power generation element of a solar cell, when the resin film of the present invention is used at a high temperature or the like, the internal conductive wires and electrodes due to moisture or water permeation. Can be prevented from occurring. Further, even in a laminated glass for heat ray reflection in which a vapor-deposited metal film is inserted between the glass and the EVA film, the generation of the color of the metal film can be suppressed in the same manner as described above. Further, the resin film of the present invention can be advantageously used in any field where the film is brought into contact with a metal.
  • the resin film of the present invention preferably contains an ethylenenoacetate butyl copolymer as a main component, and further contains additives such as a crosslinking agent, a crosslinking aid, and a silane coupling agent.
  • additives such as a crosslinking agent, a crosslinking aid, and a silane coupling agent.
  • the organic resin used for the resin film of the present invention is mainly EVA (ethylene-vinyl acetate copolymer).
  • EVA ethylene-vinyl acetate copolymer
  • a polybutyl acetal-based resin for example, polybutyl formal, polybutyl butyral (PVB resin), modified PVB
  • PVB resin polybutyl butyral
  • a vinyl chloride resin may be used in combination. It is preferable to use only EVA.
  • E VA is acetic Bulle content, generally 2 0-4 0% by weight, further 2 5-2 9 mass 0/0, and particularly preferably 2 5-2 7 mass 0/0. If the content of the butyl acetate is less than 20% by mass, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. Conversely, if the content exceeds 40% by mass, acetic acid is easily generated and For example, in the case of security glass, the impact resistance and penetration resistance tend to be insufficient.
  • the EVA can contain various additives such as a plasticizer, an organic peroxide, and an adhesion improver.
  • the plasticizer is not particularly limited, but generally an ester of a polybasic acid or an ester of a polyhydric alcohol is used. Examples thereof include octylphthalate, dihexyl / raedipate, triethyleneglycol / laze-2-ethynolebutyrate, petit ⁇ / sebagate, tetraethyleneglycol diheptanoate, and triethylene glycol diperargonate. .
  • One plasticizer may be used, or two or more plasticizers may be used in combination.
  • the content of the plasticizer is preferably in the range of 5 parts by mass or less based on 100 parts by mass of EVA.
  • the above EVA generally contains an organic peroxide or a photosensitizer as a cross-linking agent in order to suppress the generation of acetic acid and to adjust the adhesion to a glass plate or an organic polymer. Since the curability of the resin composition containing an organic peroxide is improved by heating, the film strength of the obtained film is also improved.
  • any organic peroxide can be used as long as it decomposes at a temperature of 10 ° C. or more to generate radicals.
  • the organic peroxide is generally selected in consideration of film forming temperature, composition adjustment conditions, curing (bonding) temperature, heat resistance of the adherend, and storage stability. In particular, those having a decomposition temperature with a half-life of 10 hours of 70 ° C. or more are preferred.
  • this organic peroxide examples include 2,5-dimethylhexane-1,2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl- 2,5-I-bis (t-butylperoxy) hexane 3-to-t-butylperoxide, t-butylcumylperoxide, 2,5-dimethyl-2,5-di ( ⁇ -butylperoxy) Xan, dicuminoleperoxide, a, a'-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) pallate, 2,2-bis (t-butylperoxy) butane, 1,1,1-bis (t-butylpyroxy) cyclohexane, 1,1,1-bis (t-butylperoxy) 1,3,3,5-trimethylcyclohe
  • the content of the organic peroxide is preferably 1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, particularly preferably 0.1 to 1 part by mass with respect to 100 parts by mass of EVA.
  • a photosensitizer photopolymerization initiator;
  • a photosensitizer photopolymerization initiator
  • Examples of the above-mentioned photopolymerization initiator include benzoin, benzophenone, benzoylmethinol ether, benzoinethyl ether, benzoinisopropyl ether, benzoin isoptinoleatenore, dibenzinole, 5-nitroacenaphthene, and hexane. Chlorocyclopentadiene, p-Nitrodifenoline, p-Nitroairinline, 2,4,6-Tri-troaniline, 1,2-Benzantraquinone, 3-Methyl-1,3-Diaza-1,9 One van Anthrone and the like can be mentioned. These can be used alone or in combination of two or more.
  • the EVA film according to the present invention improves various physical properties (such as mechanical properties, adhesive properties, transparency and other optical properties, heat resistance, light resistance, cross-linking speed, etc.), including suppression of acetic acid generation on the film.
  • various physical properties such as mechanical properties, adhesive properties, transparency and other optical properties, heat resistance, light resistance, cross-linking speed, etc.
  • Suitable species of such compounds By adding an appropriate amount of acetic acid, the transparency can be improved and the amount of acetic acid generated can be suppressed.
  • the acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include esters or amides of acrylic acid or methacrylic acid.
  • ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, etc., cyclohexyl, tetrahydrofurfuryl, aminoethyl, 2-hydroxyethyl, 3 —Hydroxypropynole group and 3-chloro-2-hydroxypropyl group.
  • esters of polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol with acrylic acid or methacrylic acid can also be mentioned.
  • amides include diacetone acrylamide.
  • polyfunctional compound crosslinking assistant
  • examples of the polyfunctional compound include glycerin, trimethylolpropane, pentaerythritol, and the like obtained by esterifying a plurality of acrylic or methacrylic acids, triaryl cyanurate, and triallyl isocyanurate. Triarinoleisocyanurate is preferred.
  • Epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidinole ether, aryl glycidyl ether, 2-ethylhexyl glycidyl ether, Phenyldaricidyl ether, phenol (ethylenoxy) 5 glycidinoleate ⁇ /, p-t petit ⁇ ; refeninoleregidinoleatel, diglycidyl adipate, diglycidyl phthalate, dalicidyl methacrylate And butyldaricidyl ether.
  • the above-mentioned compound that is, the acryloxy group-containing compound, the methacryloxy group-containing compound and the Z or epoxy group-containing compound, or the crosslinking assistant is usually preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of EVA. , Further 0.1 to 2 parts by mass, especially 0.1 to 1 part 5010896
  • a silane coupling agent can be added to EVA as an adhesion improver in order to further increase the adhesive force with a glass plate and a film made of an organic polymer.
  • silane coupling agent examples include ⁇ -clopropynolemethoxysilane, bierethoxysilane, vinyltris ((8-methoxetoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, burtriacetoxysilane , ⁇ —glycide Xypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, ⁇ -mercaptopropyltrimethoxysilane, -aminopropyltriethoxysilane, N—] 3- (aminoethyl) — ⁇ -aminopropinoletrimethoxysilane
  • silane coupling agents may be used alone or in combination of two or more. Is preferably 5 parts by mass or less, particularly preferably
  • the resin film of the present invention preferably contains a benzotriazole-based compound in order to reduce the amount of acetic acid extracted and prevent corrosion such as cracking.
  • a benzotriazole-based compound examples include 1H-benzotriazole, methyl 1H-benzotriazole, 1H-benzotriazole salt (eg, potassium salt, sodium salt), 1H-benzotriazole 'ammonium salt, 1H-benzene Zotriazole 'amine salts can be mentioned.
  • the content of the benzotriazole-based compound is preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of EVA. Excessive addition undesirably delays crosslinking.
  • PVB resin is a kind of ⁇ that can be used as the organic resin other than the above EVA is poly Bulle ⁇ cell tar units 70-95 weight 0 /.
  • the polyvinyl acetate units are :! In ⁇ 1 5 mass 0/0, the average polymerization degree of 200 to 3,000, preferably preferably has a 300 to 25 00, PVB resin is used as resin composition containing plasticizer.
  • the plasticizer of the PVB resin composition include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers.
  • the resin film of the present invention has an ethylene / butyl acetate copolymer as a basic structure, and is subjected to a durability promotion test in which it is left for 100 hours in an environment of 85 ° C. and 85% RH.
  • the acetic acid content is limited to very low concentrations (less than 200 ppm, preferably less than 100 ppm, especially less than 6 ppm).
  • Such a low acetic acid content can be obtained by optimizing the butyl acetate content of EVA, the type and amount of the crosslinking agent, the type and amount of the crosslinking assistant, and the like. For example, butyl acetate content 26 mass.
  • the crosslinking agent is 0.2 to 2% by mass (particularly 0.2 to 1% by mass), and the crosslinking assistant is 0.5 to 2% by mass (particularly 0.5 to 1% by mass). %), A low acetic acid concentration can be obtained by appropriately selecting these types. When a small amount of a cross-linking agent or a cross-linking assistant is used, a low acetic acid concentration is particularly advantageously obtained. It is thought to be protected.
  • the resin film (laminated glass) is extracted from the resin film by heating and refluxing by heating with water after performing a durability promotion test in which the resin film (laminated glass) is left in an environment of 85 ° C. and 85% RH for 100 hours.
  • Acetic acid is less than 200 ppm.
  • an EVA film (600 m thick) which is a resin film obtained after the durability promotion test, was cut into approximately 3 mm squares, placed in a flask with the same amount of distilled water, and a cooling tube was installed. Heat, treat at boiling reflux for 24 hours, and determine the amount of free acetic acid using ion chromatography.
  • the resin film of the present invention can be produced, for example, by a method of obtaining a sheet-like material by ordinary extrusion molding, calender molding or the like.
  • a sheet-like material may be obtained by dissolving the mixture containing EVA or the like in a solvent, applying the solution on an appropriate support with an appropriate coater (coater), and drying to form a coating film. it can.
  • the thickness of the resin film of the present invention is preferably in the range of 0.1 to 1 mm, particularly preferably in the range of 0.1 to 0.5 mm.
  • FIGS. ⁇ Examples in which the resin film of the present invention is used for solar cells and laminated glass are shown in FIGS. ⁇ This will be described with reference to FIG.
  • an ethylene monoacetate copolymer (EVA) is sealed between the glass substrate 11 as the front side transparent protective member on the light-receiving side and the back side protective member (back cover) 12.
  • the membrane (using the resin film of the present invention) 13 A, 13 B seals a solar cell, that is, a power generation element 14 such as silicon.
  • a power generation element 14 such as silicon.
  • the solar cell is obtained by subjecting the laminate to a vacuum laminator according to a conventional method, for example, at a temperature of 120 to L50 ° C, a deaeration time of 2 to 15 minutes, a press pressure of 0.5 to 1 atm,
  • a transparent adhesive layer (the resin of the present invention) can be easily manufactured by pressing under heat and pressure in a press time of 8 to 45 minutes.
  • Film is used.
  • 22 and glass plate 23 are laminated.
  • Metal deposition films 24 A and 24 B are formed on the surfaces of the glass plate 21 and the glass plate 23, and the transparent adhesive layer 22 is in direct contact therewith.
  • a resin film is sandwiched between two metal-deposited float glasses so that the vapor-deposited surface is in contact with the resin film, and this is vacuum degassed and pre-pressed. After that, the pre-pressed glass laminate is put into an oven and heat-pressed.
  • a resin composition was prepared by kneading the components shown in Tables 1 and 2 at 80 ° C using a whirling mill, and the obtained composition was sandwiched between two PET films to obtain a resin composition of 100 ° C. C, 5 minutes After press-molding under the conditions described above, the PET films on both sides were peeled off after cooling and a finolem with a thickness of 0.6 mm was obtained.
  • the resin film obtained on two pieces of float glass with silver deposited on a surface of 3 mm thickness is sandwiched so that the deposited surface is in contact with the resin film, and this is placed in a PET bag and degassed under vacuum, about 80 ° C was pre-pressed for 30 minutes. Then, the pre-pressed glass laminate is placed in an oven, and the time shown in Table 1 from the time when the surface temperature reaches 150 ° C at atmospheric pressure (30 minutes in Examples 5 and 6 and Comparative Examples 4 and 5) ) Heated to produce a laminated glass.
  • the evaluation of the obtained resin film was performed as follows.
  • the obtained 0.6 mm thick film (about 1 g) was heated at 160 ° C. for 30 minutes, and the amount of decrease in the film mass was measured.
  • the evaluation of the obtained laminated glass was performed as follows.
  • the laminated glass was left in an environment of 85 ° C. and 85% RH for 100 hours, a durability promotion test was performed, and corrosion of the deposited silver film was observed.
  • Crosslinker 0.5 1 2 2 3 2 0.5 Crosslinking aid 1 1 2 2 2 2 1 Additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Acetic acid------0.02 Heating time 30 30 30 30 30 60 30
  • EVA 1 Ethylene / vinyl acetate copolymer with a vinyl acetate content of 26% by mass
  • EVA 2 Ethylene Z-Butyl acetate copolymer with a content of 28% by mass of acetate acetate
  • Crosslinking agent 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane
  • Crosslinking aid triallyl isocyanurate
  • EVA2 Ethylene / Butyl acetate copolymer with a content of butyl acetate of 28% by mass
  • Crosslinking agent 1,1-bis (t-butylperoxy) trimethylcyclohexane
  • Crosslinking assistant triallyl isocyanurate
  • Free acetic acid concentration w Extraction amount with distilled water As shown in Tables 1 and 2, the laminated glasses of the examples were excellent in both the haze and the durability. The correlation between acetic acid concentration and durability was also obtained. Industrial applicability
  • the resin film according to the present invention has a low acetic acid content and its generation over time is small, so that when the film comes into contact with a metal, it hardly corrodes the metal. Further, since the resin film of the present invention has a low haze and a high transparency, it is required to maintain a high transparency without corroding metals (eg, a silicon power generation element of a solar cell). Sealing film and laminated glass for heat ray reflection).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Il est prévu un film de résine qui ne s’hydrolyse pas avec le temps, par exemple suite à un changement environnemental pour générer de l’acide acétique et d’une excellente transparence. Le film de résine comprend un copolymère éthylène/acétate de vinyle et se caractérise en ce qu’en laissant reposer le film de résine à une température de 85°C et une humidité relative de 85% pendant 100 heures, avant de le porter à ébullition dans l’eau, avec chauffage et refluement, la quantité d’acide acétique extraite est inférieure ou égale à 200 ppm.
PCT/JP2005/010896 2004-06-08 2005-06-08 Film de résine WO2005121227A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2006514611A JPWO2005121227A1 (ja) 2004-06-08 2005-06-08 樹脂フィルム
CN2005800186508A CN1997688B (zh) 2004-06-08 2005-06-08 树脂薄膜
US11/570,085 US20070259998A1 (en) 2004-06-08 2005-06-08 Resin Film
EP05751284A EP1783159B1 (fr) 2004-06-08 2005-06-08 Film de résine

Applications Claiming Priority (2)

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JP2004-169509 2004-06-08
JP2004169509 2004-06-08

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WO2005121227A1 true WO2005121227A1 (fr) 2005-12-22

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JP (1) JPWO2005121227A1 (fr)
CN (1) CN1997688B (fr)
WO (1) WO2005121227A1 (fr)

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JP2008205448A (ja) * 2007-01-22 2008-09-04 Bridgestone Corp 太陽電池用封止膜及びこれを用いた太陽電池
JP2008235882A (ja) * 2007-02-23 2008-10-02 Bridgestone Corp 太陽電池用封止膜及びこれを用いた太陽電池
JP2017088487A (ja) * 2015-11-12 2017-05-25 台偉 陳 中間膜を有する合わせガラス、中間膜の製造方法及び合わせガラスの製造方法
CN111403508A (zh) * 2018-12-14 2020-07-10 松下电器产业株式会社 太阳能电池组件

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EP2087526B1 (fr) * 2006-11-08 2011-12-21 Bridgestone Corporation Films d'etancheite pour cellules solaires
DE102007041055A1 (de) * 2007-08-29 2009-03-05 Lanxess Deutschland Gmbh EVM in Solarmodulen
US20100180940A1 (en) * 2009-01-20 2010-07-22 Weihong Cui Photovoltaic Module With Stabilized Polymer
US20140360582A1 (en) * 2009-01-20 2014-12-11 Solutia Inc. Thin film photovoltaic module with stabilized polymer
EP2380210A4 (fr) * 2009-01-22 2012-05-30 Du Pont Encapsulant au polyvinylbutyral comprenant des amines encombrées pour modules de cellules solaires
DE102009028118A1 (de) * 2009-07-30 2011-02-03 Schott Ag Photovoltaikmodul mit verbesserter Korrosionsbeständkigkeit und Verfahren zu dessen Herstellung
DE102009036533A1 (de) * 2009-08-07 2011-02-10 Lanxess Deutschland Gmbh Verfahren zur Herstellung von Solarmodulen
DE102009036534A1 (de) 2009-08-07 2011-02-10 Lanxess Deutschland Gmbh EVM-Granulat
CN102811854A (zh) * 2010-03-19 2012-12-05 首诺公司 具有稳定化聚合物的光伏打模块
TWI498213B (zh) * 2010-03-25 2015-09-01 Solutia Inc 具有穩定化聚合物之光伏打模組
JP5975447B2 (ja) * 2012-03-16 2016-08-23 パナソニックＩｐマネジメント株式会社 太陽電池モジュール
CN104465830A (zh) * 2014-12-17 2015-03-25 苏州费米光电有限公司 耐腐蚀太阳能板
ES2632783T3 (es) 2014-12-19 2017-09-15 Evonik Degussa Gmbh Sistemas de redes de cubierta para láminas de encapsulación que comprenden compuestos de bis-(alquenilamidas)
ES2633243T3 (es) * 2014-12-19 2017-09-20 Evonik Degussa Gmbh Sistemas de agentes de reticulación conjunta para películas de encapsulación que comprenden compuestos de (met)acrilamida
ES2635260T3 (es) 2014-12-19 2017-10-03 Evonik Degussa Gmbh Sistemas correticulantes para láminas de encapsulado que comprenden compuestos de urea

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JPS57196747A (en) * 1981-05-29 1982-12-02 Bridgestone Corp Laminated glass
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JPS62148509A (ja) * 1985-12-23 1987-07-02 Bridgestone Corp 透明膜を有する積層物
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JPH0872199A (ja) * 1994-09-06 1996-03-19 Bridgestone Corp 透明遮音板
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JP2002368243A (ja) * 2001-06-11 2002-12-20 Bridgestone Corp 太陽電池
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Publication number Priority date Publication date Assignee Title
JP2008205448A (ja) * 2007-01-22 2008-09-04 Bridgestone Corp 太陽電池用封止膜及びこれを用いた太陽電池
JP2008235882A (ja) * 2007-02-23 2008-10-02 Bridgestone Corp 太陽電池用封止膜及びこれを用いた太陽電池
EP2117049A1 (fr) * 2007-02-23 2009-11-11 Bridgestone Corporation Feuille d'hermétisation de cellule solaire et cellule solaire utilisant celle-ci
EP2117049A4 (fr) * 2007-02-23 2012-11-07 Bridgestone Corp Feuille d'hermétisation de cellule solaire et cellule solaire utilisant celle-ci
JP2017088487A (ja) * 2015-11-12 2017-05-25 台偉 陳 中間膜を有する合わせガラス、中間膜の製造方法及び合わせガラスの製造方法
CN111403508A (zh) * 2018-12-14 2020-07-10 松下电器产业株式会社 太阳能电池组件

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Publication number Publication date
CN1997688B (zh) 2010-12-29
EP1783159A1 (fr) 2007-05-09
CN1997688A (zh) 2007-07-11
EP1783159A4 (fr) 2009-08-19
JPWO2005121227A1 (ja) 2008-04-10
US20070259998A1 (en) 2007-11-08
EP1783159B1 (fr) 2012-02-29

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